Generalized unitary coupled cluster excitations for multireference molecular states optimized by the Variational Quantum Eigensolver

TL;DR

This paper explores advanced unitary coupled cluster ans"atze within the variational quantum eigensolver framework to accurately compute excited states of molecules, including multireference states, on near-term quantum computers.

Contribution

It introduces modified UCC ans"atze tailored for excited states and demonstrates their effectiveness in calculating molecular energy curves with high accuracy.

Findings

VQE with new ans"atze accurately reproduces classical full configuration interaction results.

Modified UCC methods prevent spin symmetry crossover during optimization.

The approach works for various molecules and electronic states, including multireference cases.

Abstract

The variational quantum eigensolver (VQE) algorithm, designed to calculate the energy of molecular ground states on near-term quantum computers, requires specification of symmetries that describe the system, e.g. spin state and number of electrons. This opens the possibility of using VQE to obtain excited states as the lowest energy solutions of a given set of symmetries. In this paper, the performances of various unitary coupled cluster (UCC) ans\"atze applied to VQE calculations on excited states are investigated, using quantum circuits designed to represent single reference and multireference wavefunctions to calculate energy curves with respect to variations in the molecular geometry. These ans\"atze include standard UCCSD, as well as modified versions of UCCGSD and k-UpCCGSD which are engineered to tackle excited states without undesired spin symmetry cross-over to lower states during VQE optimization. These studies are carried out on a range of systems including H$_2$, H$_3$, H$_4$, NH, and OH$^{+}$, CH$_2$, NH$^{+}_{2}$, covering examples of spin singlet, doublet and triplet molecular ground states with single and multireference excited states. In most cases, our calculations are in excellent agreement with results from full configuration interaction calculations on classical machines, thus showing that the VQE algorithm is capable of calculating the lowest excited state at a certain symmetry, including multireference closed and open shell states, by setting appropriate restrictions on the excitations considered in the cluster operator, and appropriate constraints in the qubit register encoding the starting mean field state.